Process for production of lithium battery electrodes from brine

ABSTRACT

A method of manufacturing electrodes from a lithium-containing brine, said method comprising the steps of: providing an electrochemical cell comprising at least a cathodic chamber filled with a lithium-containing brine; contacting a lithium-intercalating electrode material with the lithium-containing brine; applying an electrical current to the cell for a duration sufficient to allow intercalation of lithium from the brine onto electrode material; and stopping the electrical current.

FIELD OF THE INVENTION

The technical field relates to the extraction of lithium from brines anda process for the mass production of lithium battery electrodes.

BACKGROUND OF THE INVENTION

Lithium ion batteries have emerged to become the dominantelectrochemical energy storage technology due to their ability toprovide high specific energy density and charging behavior over hundredsto thousands of recharge cycles. The accelerating production of electricvehicles, renewable energy storage systems, drones, electronics androbotics suggests the demand for batteries and hence new lithium sourcesand extraction processes must be developed to meet increasing demand.

Existing lithium production techniques from brines generally consist oftwo steps: the lithium content is first concentrated then transformedinto a solid product for sale. Traditional techniques for theconcentration of lithium include evaporation ponds, solvent extraction,membrane filtration, adsorption, selective precipitation and others butall seek to produce a liquid stream concentrated in lithium. In generalcaustic soda or similar alkali is added to the concentrated lithiumsolution to precipitate lithium carbonate or a similar lithium salt forsale. These processes often have high operational costs due toconsumables such as acids or bases to changes pH, adsorbents which cangranulate after multiple cycles or highly selective but expensivemembranes which can quickly foul.

Brines comparable in composition to those found in the Lithium trianglehave been discovered in produced oil field waters from evaporitecarbonate reservoirs. Water treatment operations are ubiquitous toupstream facilities for the treatment of produced waters beforereinjection or disposal. Consequently, over a hundred years of technicalexperience has accrued in this industry regarding the treatment ofproduced waters and the intention of this patent is to adapt theseoperations to extract lithium from brines in the form of a lithiatedelectrode material using the same principles which guide rechargeablelithium battery operation.

Common lithium ion battery electrode materials include metal oxides suchas LiCoO₂, LiMn₂O₄, LiFePO₄, sulfur or potentially pure lithium metal ona support for the cathode coupled with an anode comprised of graphite,nickel or other potential materials depending on the desired anodicreaction, cell operating voltage, etc. Currently around half of batteryprices derive from the cost of their electrodes and this has thepotential to increase as strategic resources such as lithium or rareearth metals see increased demand as battery use proliferates.

Several strategies for the electrochemical extraction of lithium frombrines have developed over the last decade. Electrodialysis systemsoften rely on lithium selective membranes to allow lithium to cross froman anodic chamber into a cathodic chamber to produce a relativelyconcentrated lithium stream in the catholyte. The lithium selectivemembranes are often advanced materials such as ion-impregnated organicframeworks, metal-organic frameworks and similar as cheaper membranesused in lithium batteries do not possess sufficient lithium selectivity.These new membrane technologies can experience operational issuesrelated to fouling and poor cycling performance, which has prompted someresearchers to attempt electrodialysis systems which separate other ionsfrom the lithium-containing brine to better facilitate downstreamprocessing steps.

Recent research has moved towards electrochemical lithium extractionsystems which more closely resemble lithium batteries duringcharging/discharging in order to take advantage of cheaper, morecommercially abundant materials. These processes involve contactingtraditional metal oxide electrodes with brine on the cathode sidewhereby lithium is intercalated into the metal oxide crystallinelattice. Once the cathodes are fully saturated with lithium, the anolyteand catholyte flow streams are swapped and the lithium-bearingelectrodes are now turned to anodic operation such that they generate alithium-enriched stream for further processing into a salt product suchas lithium carbonate or lithium hydroxide.

Presently, the lithium ion battery production supply chain consists ofthree types of businesses. Tier 1 suppliers produce lithium salts fromore or brine resources while Tier 2 suppliers create intermediatebattery components such as ion exchange membrane separators orelectrolytes. Tier 3 suppliers purchase the lithium salt to producetheir battery electrodes and assemble the final lithium batteryproduction with the additional inputs from Tier 2 suppliers. The processdescribed herein this patent consolidates this supply chain to producebattery ready electrode products directly from lithium resources on sitefor the production of lithium ion batteries.

There is thus a very real need for a more efficient method of preparinglithium electrodes which overcomes at least one of the drawbacks of theprior art.

SUMMARY OF THE INVENTION

According to the present invention, extraction of lithium from brines isachieved by introduction of electrode materials to a pre-processed brinestream such that lithium-containing electrodes can be mass produced fora wide range of battery applications and requirements.

According to one aspect of the present invention, there is provided amethod of manufacturing electrodes from a lithium-containing brine, saidmethod comprising the steps of:

providing an electrochemical cell comprising at least:

-   -   a cathodic chamber filled with a lithium-containing brine;

immersing a lithium-intercalating electrode into said brine in thecathodic tank;

applying an electrical current to the electrochemical cell for aduration sufficient of time for lithium ions present in thelithium-containing brine to be reduced and be deposited onto theelectrode material.

Preferably, the method further comprises the step of pre-processing thelithium-containing brine to remove at least one contaminant prior tofilling it into the cathodic chamber.

Preferably also, the electrode is a thin film. More preferably, theelectrode film is in the form of a roll and which is positioned on aconductive substrate as the electrode is fed into the brine solution ofthe electrochemical cell.

According to a preferred embodiment, the electrode film is lithiumdeficient prior to the immersion into the lithium-containing brine inthe cathodic tank

Preferably, the lithium-intercalating electrode is incorporated into atleast one tray which has a plurality of wells of a predetermined shape,said well being adapted for the deposition of electrode materials.

According to a preferred embodiment, the pre-processing step involves atleast one of the following operations:

removing dissolved gases in the produced fluid near the formationtemperature in a crystallizer or similar vessel;

precipitating saturated carbonates;

removing any produced fines/sand.

removing hydrocarbons or other organic contaminants from the producedbrine by using settling tanks and/or froth flotation and/or filtration;

removing halites and/or other potential highly saturated salts or silicawhich don't possess retrograde solubilities by using a secondcrystallizer at reduced temperature;

re-heating the brine before entering the electrochemical cell to improvekinetics, reduce saturation indices and possibly re-collect heat lost inthe second, cooler crystallization step.

According to another aspect of the present invention, there is provideda system to perform lithium extraction from lithium-containing brines,said system comprising:

a cathodic tank allowing the insertion and removal of electrode traysthereinto;

electrodes integrated into a stack electrical system with connection toan anodic chamber to produce an electrochemical cell.

Preferably, the system operates in a semi-continuous or batch-wisemanner. Preferably also, the cathodic chamber is filled with lithiumcontaining brine.

According to a preferred embodiment, the anodic chamber is entirely orpartially decoupled from the cathodic chamber such that it has adistinct electrolyte composition not derived from the brine but insteaddesigned to conduct a particular anodic reaction on an appropriateanodic electrode surface.

According to another aspect of the present invention, there is provideda system to perform lithium extraction from lithium-containing brines,said system comprising:

a cathodic tank allowing the insertion and removal of electrode traysthereinto;

a lithium-containing brine to be placed in the tank; and

at least one electrode integrated into a stack electrical system withconnection to an external energy source to produce an electrochemicalcell.

According to another aspect of the present invention, there is provideda method of mass producing lithium-intercalated electrodes from alithium-containing brine proximate the mining site of saidlithium-containing brine, said method comprising the steps of:

obtaining said lithium-containing brine from a natural source;

removing contaminants from said brine;

providing an electrochemical cell comprising at least:

-   -   a cathodic chamber;

filling the cathodic chamber with said the decontaminatedlithium-containing brine;

immersing a lithium-intercalating electrode into said brine in thecathodic tank;

applying an electrical current to the electrochemical cell for aduration sufficient of time for lithium ions present in thelithium-containing brine to be reduced and be deposited onto theelectrode material.

Preferably, the step of removing contaminants from said brine comprisesat least one of the operations selected from the group consisting of:removing dissolved gases in the produced fluid near the formationtemperature in a crystallizer or similar vessel; precipitating saturatedcarbonates; removing any produced fines/sand; removing hydrocarbons orother organic contaminants from the produced brine by using settlingtanks and/or froth flotation and/or filtration; removing halites and/orother potential highly saturated salts or silica which don't possessretrograde solubilities by using a second crystallizer at reducedtemperature; and re-heating the brine before entering theelectrochemical cell to improve kinetics, reduce saturation indices andpossibly re-collect heat lost in the second, cooler crystallizationstep.

According to a preferred embodiment of the present invention, there isdescribed a method to produce large numbers of electrodes, send them tothe lithium resource and produce them on-site for the purpose of batterymanufacturing. In general, the process described in this patent can beunderstood to some extent as being an adaptation of a prior art processbut rather than having lithium enter the electrodes then swapping theflow pathways to produce a concentration lithium stream thelithium-saturated electrodes are instead replaced continuously withunsaturated electrodes.

An advantage of this process is that it eliminates potentially severalintermediate steps which would otherwise be necessary in the life cyclefrom lithium resource in-situ to a finished battery product. In thetypical process a lithium salt is produced from a brine or ore resourcewhich requires separating the lithium ions from a mixed salt solutionand processing the concentrated lithium stream into a salt product whichis then shipped to battery manufacturers to produce lithium-containingelectrodes and electrolytes.

Another advantage of this process is that it provides a flexible,scalable platform for the creation of battery electrodes with entirelydissimilar materials, properties, dimensions, etcetera but can beproduced in parallel with each other to finally become lithium saturatedtogether as part of the cathodic chamber electrode tray stack.

According to a preferred embodiment of the present invention, trays orsimilar modular, layered units are prepared to produce conductive platesor wells with specified dimensions which can be used with a chosenelectrode synthesis technique and material to produce large sheets ofelectrodes which can be integrated into an appropriately designedelectrochemical process system. Lithium containing brine resources arefirst pre-processed to remove contaminants such as hydrocarbons,precipitants, and potentially others before entering a cathodic tankcontaining the fabricated electrode trays. In cathodic operation, theseelectrodes intercalate lithium and following a sufficient residence timethe trays can be removed together for shipment. The trays can then bedismantled, recycled and the lithium-bearing electrode plates recoveredfor immediate use in battery production.

According to a preferred embodiment, the electrode trays are to bedesigned in a modular, customizable fashion such that any design ofelectrode shape, material, conductive backing, etcetera can be createdon a tray or similar platform which can be stacked with similar trayscontaining different electrodes to match customer design requirements.These trays can inexpensively be designed to be unique usingcomputer-aided design programs then manufactured using traditionalmethods or using emerging automated techniques such as 3D printing,lithography, robotics or similar.

Battery manufacturing is a mature industrial field and as such there area number of techniques for the synthesis of electrode materials, each ofwhich requires slightly or significantly different process operation andinputs. Some examples include electrostatic spray deposition, sol-gelmethod, coating of inert, porous substrates with conductive layers,conductive fibres or foams, nanoparticulate and/or micropatternedelectrode substrates and many others which could be implemented in theprocess proposed herein. In general, the prepared electrode trays arefilled with an appropriate electrode material and processed to produce afinal product ready for the field.

According to a preferred embodiment of the present invention,pre-processing of the brine is in general necessary to minimize foulingof the electrochemical system and any potential contamination of theelectrode product. One preferred embodiment comprises of an initialde-gassing of the produced fluid near the formation temperature in acrystallizer or similar vessel to remove dissolved gases whileprecipitating saturated carbonates and removing any produced fines/sand.Preferably, hydrocarbons or other organic brine contaminants would alsohave to be removed by methods such as settling tanks, froth flotation,filtration, etc. This solution can then move to a second crystallizer atreduced temperature which can drop out halite and other potential highlysaturated salts or silica which don't possess retrograde solubilities.Finally, the brine could be slightly re-heated before entering theelectrochemical system to improve kinetics, reduce saturation indicesand possibly re-collect heat lost in the second, cooler crystallizationstep. The particular brine pre-processing embodiment can varyconsiderably depending on the brine composition and properties, the onlycriteria is that the brine must be made chemically suitable to avoidfouling or contamination of the electrochemical system.

Many potential embodiments of the electrochemical system exist can beused, but it is preferable that there be a large cathodic tank with amechanical design such that the fabricated electrode trays can be loadedinto and out of the tank on a regular basis and the electrodesintegrated into a stack electrical system with connection to an anodicchamber or similar electron source to produce an electrochemical cell.According to a preferred embodiment, in a semi-continuous or batch-wisemanner the cathodic chamber is filled with brine and operated atrelatively low cathodic voltage as set by a potentiometer,electrochemical control system or similar to minimize contaminatingsodium intercalation into the electrode product as well as overpotentiallosses. Design of the anodic reaction is flexible and depends oneconomic and operational choices with respect to how much energy theelectrochemical cell will consume or generate, whether the anodicreaction is compatible with brine as an anolyte or with a partially orentirely separate anolyte tank and composition. The anode and cathodechambers can be connected by an ion exchange membrane using any choiceof cationic, anionic or other selectivity or designed to functionseparately given modifications to account for pH drift during operation.Once the cathodic electrode trays have sufficiently charged with lithiumthe system is put into a safe operating mode, drained, opened and theelectrode trays removed for distribution and disassembly. Freshelectrodes are installed into the cathode tank system and the processrepeated to produce large quantities of prepared electrodes for lithiumion batteries.

According to one embodiment of the present invention, the methodcomprises the following elements:

a. Manufacturing of the electrode tray, either by automated 3D printing,traditional techniques such as ‘calendaring’ or a combination. This trayconsists of wells corresponding to the desired electrode dimensions,ideally with a copper, aluminum or similar electron collector at thewell base which are electrically connected to the tray edge. Solutioncontaining the desired electrode components such as FeCl3 and H3PO4salts, with some polymeric binder and conductive additives, can be mixedthen poured into the electrode moulds which could be hydraulicallyconnected via raised channels connecting the wells. Other manufacturingmethods may be substituted such as automated spray deposition,lithography, atomic layer deposition, etcetera to achieve differentelectrode materials, properties and performance.

b. The electrode tray wells now must be filled with the desiredelectrode material precursors and transformed into a solid electrode onthe current collector plates by a chosen electrode synthesis technique.This step can take different forms depending on the desired finalcathode product, ultimately the trays must be prepared for shipment tosite, potentially protected by a covering and the electrodes need to bein a condition such that they're ready for introduction into the brinecathode compartment.

c. At the brine source, which may or may not be where the electrodetrays are prepared, the brine is first pre-processed in order to removecontaminants, organic foulants and precipitating minerals which couldfoul the electrode trays or the electrochemical system generally.

d. Electrode trays are then introduced into a large cathodic tank whichsemi-continuously fills the tank with brine and electrically connectedto the anodic chamber electrodes.

e. Voltage is applied or generated over a residence time necessary tofully saturate the cathodic electrode with lithium from the brinesolution.

f. Following a sufficient residence time to saturate the electrodeplates with intercalated lithium ions it should then be possible toremove the trays together, dry them and otherwise prepare them forshipment. Either the manufacturer or the customer could then disassemblethe trays, return them for recycling and collect their custom designedelectrodes.

According to a preferred embodiment of the present invention, during theelectrode production process, at any appropriate point between steps a-fit may be beneficial to introduce additives to the electrodes such asdoping agents, nanoparticles or similar to affect the final electrodecomposition and consequently its ultimate performance.

According to another embodiment of the method, the anodic compartment isconverted into a microbial fuel cell whereby agricultural and otherbiological wastes could be introduced to the anodic tank and oxidized byheterotrophic, electrogenic microbial communities which can survive asbiofilms on the electrode surface and use it as a sink for respirativeelectrons. The advantage of this technique is that it can simultaneouslygenerate electricity and compost wastes into fertilizers whileextracting lithium/producing lithium battery electrodes.

According to another embodiment of the method, the anodic chamber isentirely or partially decoupled from the cathodic chamber such that ithas a distinct electrolyte composition not derived from the brine butinstead designed to conduct a particular anodic reaction on anappropriate anodic electrode surface. Or the anodic tank is notincluded, and electrons are provided for the cathodic reaction by anexternal energy source rather than an anodic reaction.

According to another embodiment of the method, instead of extractinglithium from a natural or oil field produced brine this technique can beextended to any wastewater, blowdown or leachant stream which containsan economically sufficient lithium content. This process can beimplemented in parallel with and connected to existing oil field,chemical, wastewater or similar process operations.

According to another embodiment of the method, the lithium-intercalatingelectrode material exists on a current collector backing in the form ofa roll or similarly continuous sheet, which can be wound around a spool,spindle or similar and potentially incorporated into a cartridge orother container to minimize environmental contamination as well asfacilitate transport, loading and unloading of the electrode roll fromthe electrochemical system described herein. The electrode roll can thenbe fed into and through an appropriately designed electrochemicalsystem, passing over a current collector plate which applies a fixedcurrent density and/or voltage such that lithium from lithium-containingbrine is intercalated into the electrode as it passes through thesystem.

According to another embodiment of the method, a reference electrode ofsufficient size and capacity is incorporated into the electrochemicalsystem to provide better control over operating voltages.

BRIEF DESCRIPTION OF THE FIGURES

Features and advantages of embodiments of the present application willbecome apparent from the following detailed description and the appendeddrawing, in which:

FIG. 1 is a diagram exemplifying one embodiment of the present inventionfor electrochemically extracting lithium from brine.

FIG. 2 illustrates a preferred embodiment of the first steps of theprocess of the present invention whereby electrode trays are prepared.

FIG. 3 illustrates a preferred embodiment of the process of the presentinvention to produce lithium battery electrodes.

FIG. 4 illustrates a preferred embodiment of the process of the presentinvention whereby lithium-intercalating electrodes are produced in anelectrochemical unit operation using the roll to roll method.

FIG. 5 illustrates a preferred embodiment of the process of the presentinvention whereby lithium-intercalating electrodes are produced in anelectrochemical unit operation using the roll to roll method without anincorporated membrane.

FIG. 6 illustrates a preferred embodiment of the process of the presentinvention whereby the roll-to-roll electrochemical electrode productionmethod described herein is scaled up.

Exemplary embodiments of the present invention will now be describedwithin.

DETAILED DESCRIPTION

Throughout the following description, specific details are set forth inorder to provide a more thorough understanding to persons skilled in theart. However, well known elements may not have been shown or describedin detail to avoid unnecessarily obscuring the disclosure. The followingdescription of examples of the invention is not intended to beexhaustive or to limit the invention of the precise forms of anyexemplary embodiment. Accordingly, the description and drawings are tobe regarded in an illustrative, rather than a restrictive, sense.

The present description describes and relates to the extraction oflithium from brines to produce lithiated electrodes for batterymanufacturing.

An advantage to the described production process is in its ability toprovide a flexible range of products at scale. Each electrode well traywill contain cathodic or anodic with particular materials, dimensions,crystal structure, synthesis process, specific surface area, etceterawhich can be manufactured by some form or combination of traditionalplastic processing, 3D printing, automated lithography, etceteraaccording to desired specifications. Trays with different electrodes canthen be stacked together in the cathodic brine compartments toaccumulate lithium and can subsequently be removed and shipped as astack. Therefore, many parallel electrode production streams can beoperated simultaneously according to orders from clients, e.g. carbattery electrode trays can intercalate lithium beside smaller dronebattery electrode trays with the only cost being an increase inoperational difficulty due to a more heterogenous electrode polarizationgeometry which will affect the systems overpotential. However, as thegoal of this system is not to operate an ideal electrochemical system somuch as saturate the cathodes this may manifest as a slight increase innecessary residence times, power consumption, etc.

As an example of electrode material fabrication methods, one preferredtechnique to produce a lithium-intercalating electrode material, ironphosphate, is to collect natural or genetically modified microbes fromeutrophic aquatic ecosystems or wastewater treatment systems which havehigh phosphate concentrations contained within their cell membranes andintroduce them into a solution containing Fe³⁺ ions. Some of the ionsform intermediate complexes within and outside the cell membrane insolution before the system is dried overnight at 80° C. before beingheated to 600° C. for 5 hours. The final product is a porous, thin filmof FePO₄ with a small C content from the combusted cells. Such anelectrode has demonstrated competent discharge capacity, a uniquenanoparticulate microstructure from biological complexation and stablecycling performance suggesting that this or similar biotechnologicaltechniques may be integrated into the electrode production processdescribed herein. The advantage of such processes is that they utilize acheap, available source of a desired compound, in this case phosphate,which would otherwise be an ecological hazard if in overabundance, andnaturally remove this contaminant from the environment to produce avalue-added product with potentially even superior performancecapability.

According to another embodiment of the method, the electrode synthesismaterials and techniques can fundamentally alter the initial electrodeproduction process as described herein. An example of such would be thetransition to a microwave synthesis process whereby microwave systemsreplace part or all of the traditional thermal drying and annealingsteps. Such processes have demonstrated initial progress in proving amore uniform heating while reducing energy use and the necessary processtime. Nanoparticulate, micropatterned, foam, conductive polymer gel, andsimilar emerging electrode material architectures can require additionalprocessing steps and inputs not otherwise described herein.

In addition to being general to the cathodic lithium-intercalatingelectrode material chosen, the present description provides a multitudeof potential anodic configurations, each of which possessing their ownoperational and economic advantages. The anodic electrode material andreaction should be considered an important degree of freedom in thedesign of this system, which can not only regulate how effectively theelectrochemical system is able to extract lithium but can also determinewhether the system as a whole consumes or produces energy. Shouldsufficiently robust electrode materials come available for industrialapplication it could be possible to evolve H₂ using a nickel anode or asimilar method, generate oxygen or chlorine gas or a variety of similarvalue-added reduction products in the anodic tank. The electrodeproduction technique described herein should also be understood toinclude anode electrode production as well, which would necessitate amodified design depending on electrolyte composition, anodic materialand reaction, etc. According to another embodiment of the method,cathodic lithiation using this technique can be performed without acoupled anodic chamber but with a direct stream of electricity producedfrom other sources to the cathodic electrodes. Such a system canexperience larger variation in cathodic chamber pH which may affectelectrode stability, for example, but after lithium extraction, thedepleted brine can be disposed similarly.

The pre-processing system design is dependent on the feedstockcomposition and properties, potential integration into existingprocesses, as well as the nature and abundance of components in thefeedstock which can pose unique operational issues or contaminationthreats with respect to the electrochemical system and product. Forexample, depending on the risk of carbonate precipitation it may benecessary to incorporate larger unit operations into the pre-processingsystem such as a Hot Lime Softener (HLS). Ideally, this step should beavoided to minimize the requirement for additional process inputs suchas soda lime and to maintain the brine stream pH within acceptableranges that will not compromise factors such as electrode stability.

FIG. 1 illustrates a first preferred embodiment of the process describedherein whereby produced brines (11) are pre-processed (10) to removepotential contaminants (exiting at 13) of the electrochemical systemincluding hydrocarbons, precipitating salts and reservoir gases. Thiscan be accomplished using a combination of typical oil field and similarwater processing unit operations such as crystallizers, separationtanks, froth flotation tanks, membrane filtration, after filters,solvent extraction, etcetera. The decontaminated brine (15) is then usedto fill a cathodic tank containing the fresh electrode trays and over acertain residence time during which electricity is added or removed fromthe system cell (23), the lithium intercalates into the electrodematerial to produce a saleable product. In this embodiment, thelithium-depleted brine is subsequently used to fill the anode tank totake advantage of low input requirements and the excellent electrolyticproperties of the highly saline brine. The anode tank (21) and cathodetank (17) can be connected by an anionic exchange membrane (19) whichwould allow chloride ions to pass into the anolyte. In this example, thechloride oxidation reaction could take place on the anodic electrode toprovide electrons for the cathode and produce another saleable productin the form of chlorine gas (25). The de-lithiated brine (27) is removedfrom the tank.

The profitability of this such a system depends in large part in therelative cost and operability of the anodic electrode which for thechloride oxidation reaction is often platinum, hence the motivation toseek alternative anodic systems which can be compatible with the brineor similarly cost-effective anolytes which can reduce power consumptionor generate power or value-added products or services in addition to thecathodic lithium extraction. Once most of the lithium has been removedfrom the brine and assuming the pre-processing steps brought the brinesinto compliance with regulatory standards the brine can then be sent fordisposal.

FIG. 2 illustrates the initial steps wherein electrode trays (201) aremanufactured with customized specifications (alternative embodiments 205and 207) but, in general, contain wells (203) or plates with conductivebacking (213) upon which electrode materials can be deposited such thata separable but intact electrode product can ultimately be created. Asimple example of an electrode material (210) and accompanying synthesisprocess would be the thermal production of FePO4, which can beaccomplished by introduction of iron chloride and phosphoric acidsolution into the wells. Then the trays (201) could be dried at 80-100°C. followed by annealing at 500-800° C. in an oven (220) for 5-12 hoursdepending on the synthesis process requirements to produce a crystallineproduct with appropriate charge and discharge performance.

FIG. 2 illustrates a common intermediate step in the production ofelectrode materials for batteries. The fabricated electrode trays (201)can be stacked and dried, then annealed together in air driers, ovens(220) or autoclaves.

FIG. 3 illustrates a preferred embodiment for the electrochemical system(313) which will remove lithium from the produced brine by absorbingthose ions into cathodic electrode material. The pre-processed brine(301) is fed into the cathode tank (307) which has been loaded with afresh electrode tray stack (311). The cathode tank (307) is separatedfrom the anode tank (309) by an anionic exchange membrane (305). Theelectrochemical cell system must be designed such that the electrodetray stacks are accessible, potentially by draining and opening theentire tank during every cycle of operation. The electrode tray stackswill have to rest on a rack or similar support system which issufficiently easy to remove and replace trays. The trays (321) will alsohave to have some form of electrical connection around their outer edgeor similar such that they can be electrically connected and integratedinto the entire electrochemical cell (313) system as a stack. For aperiod of time, the electrochemical cell (313) is operated such that thecathodic lithium battery electrode charging reaction is able to takeplace and the brine becomes depleted in lithium. Once depleted ofresource in this embodiment, the brine (see arrow 340) is reused asanolyte in the anode tank (309) before disposal (303) to take advantageof the high conductivity of brine and replacing the need for creatingartificial electrolyte solutions.

FIG. 3 also illustrates how freshly fabricated electrode trays (311)which do not contain lithium are used to replace the lithium saturatedelectrodes following the necessary residence time.

FIG. 3 also illustrates the final step whereby the electrode tray stacks(331) are removed from the electrochemical system by a forklift, crane,or similar automatic or manual system to transport them for sale anddistribution.

FIG. 4 illustrates a preferred embodiment for the electrochemical systemwhich will remove lithium from the produced brine by intercalation intoa suitable electrode material. In this embodiment, thelithium-intercalating material exists on a current collector backingwhich is in a roll (403) on a spindle and/or incorporated into asuitable cartridge which can be loaded into the unit operation and fedinto the electrochemical system with assistance of a spool with a gear,such as the feed gear (404), which can assist the electrode tape stay inalignment as it feeds with the gear teeth gripping perforations in theelectrode tape edge, similar to photographic film. The electrode tape(420) then feeds into the cathodic chamber filled withlithium-containing brine through the input (411) through rollers orsimilar before contacting the cathodic current collector (406) at whichtime lithium is intercalated into the electrode material, after whichthis electrode tape is then fed out of the anolyte chamber by the outputgear (407) onto the output roll (408). The cathodic current collector(406) is connected to an electrochemical control system (ECS) (401)which determines the operating voltage and/or current in theelectrochemical system, in addition to connecting the cathodic currentcollector (406) to the anodic current collector (402), completing theelectrochemical circuit. In this embodiment, separating the anodic andcathodic containers is a membrane (405) such as an anion exchangemembrane which can help maintain relatively constant pH during theelectrochemical process to preserve electrode material stability. Thelithium-depleted brine is removed from the system through the output(413). The anode tank is filled with a dilute aqueous solution (415).

FIG. 5 illustrates a preferred embodiment for the electrochemical systemwhich will remove lithium from the produced brine by intercalation intoa suitable electrode material without incorporation of an internalmembrane and/or separator. In this embodiment, hydrogen gas (560) is fedinto the system to act as an electron donor via decomposition intoprotons on an appropriate anode (502). Current between the anode andcathode flows through an electrochemical control system, whichinterfaces with the overall distributed process control system and actsto manage the system's operating voltage and/or current density, withthe assistance of a potentiostat system or similar, potentiallyincorporating a suitably designed reference electrode either in thebrine chamber or in a separate electrolyte chamber. An electrode roll(503) is fed into the system with gear (504) and is passed over cathodiccurrent collectors incorporated into spools over which the electrodetape (520) passes, causing intercalation of lithium from the brine intothe electrode material. The electrode tape is then reeled in with gear(507) into roll (508). An agitator (530) is present in order to maximizethe distribution of ions in the solution. The lithium-containing brineis inserted into the system via piping (501), the lithium-depleted brineis removed from the system via output piping (551).

FIG. 6 depicts a preferred embodiment for scaling up the electrochemicalsystem described herein by arranging the cathodic chamber (606) andanodic chamber (602) in such a way as to resemble a conventionalelectrochemical cell stack. As in FIG. 4, the electrode material (620)on a current collector backing is fed into the system from a roll (603)by revolution of a spindle, spool or similar, potentially with theassistance of gears, perforations in the tape for gear teeth, rollersand other equipment designed for the management of tape being fedthrough a system. The electrode tape then passes over a currentcollector which is connected to an electrochemical control system (ECS)which ensures cathodic operation such that the electrode materialintercalates lithium from lithium-containing brine in the cathodechamber, filled and drained by piping and an associated system not shownfor the sake of clarity. The ECS ensures coupling between the cathodiccurrent collectors and an associated anodic electrode for each cell inthe stack, itself conducting an anodic reaction using an appropriateelectrode material in contact with a particular anolyte composition. Inthis particular embodiment, upon becoming fully intercalated withlithium the produced electrode tape is then fed through a cleaningsystem which uses a combination of chemical and physical mechanisms forremoving contaminants which may have adsorbed themselves to theelectrode surface during contact with the brine in the cathodic chamberbefore being fed onto a product roll (608).

Although various embodiments of the invention are disclosed herein, manyadaptations and modifications may be made within the scope of theinvention in accordance with the common general knowledge of thoseskilled in this art. Such modifications include the substitution ofknown equivalents for any aspect of the invention in order to achievethe same result in substantially the same way. Numeric ranges areinclusive of the numbers defining the range. The word “comprising” isused herein as an open-ended term, substantially equivalent to thephrase “including, but not limited to”, and the word “comprises” has acorresponding meaning. As used herein, the singular forms “a”, “an” and“the” include plural referents unless the context clearly dictatesotherwise. Thus, for example, reference to “a thing” includes more thanone such thing. Citation of references herein is not an admission thatsuch references are prior art to the present invention. Any prioritydocument(s) and all publications, including but not limited to patentsand patent applications, cited in this specification are incorporatedherein by reference as if each individual publication were specificallyand individually indicated to be incorporated by reference herein and asthough fully set forth herein. The invention includes all embodimentsand variations substantially as hereinbefore described and withreference to the examples and drawings.

1. A method of manufacturing electrodes from a lithium-containing brine,said method comprising the steps of: providing an electrochemical cellcomprising at least: a cathodic chamber filled with a lithium-containingbrine; immersing a lithium-intercalating electrode into said brine inthe cathodic tank; and applying an electrical current to theelectrochemical cell for a duration sufficient of time for lithium ionspresent in the lithium-containing brine to be reduced and be depositedonto the electrode material.
 2. The method according to claim 1, furthercomprising the step of pre-processing the lithium-containing brine toremove at least one contaminant prior to filling it into the cathodicchamber.
 3. The method according to claim 1, wherein the electrode is athin film.
 4. The method according to claim 3, where the electrode filmis in the form of a roll and which is positioned on a conductivesubstrate as the electrode is fed into the brine solution of theelectrochemical cell.
 5. The method according to claim 3, wherein theelectrode film is lithium deficient prior to the immersion into thelithium-containing brine in the cathodic tank
 6. The method according toclaim 3, wherein the lithium-intercalating electrode is incorporatedinto at least one tray which has a plurality of wells of a predeterminedshape, said well being adapted for the deposition of electrodematerials.
 7. The method according to claim 2, wherein thepre-processing step involves at least one of the following operations:removing dissolved gases in the produced fluid near the formationtemperature in a crystallizer or similar vessel; precipitating saturatedcarbonates; removing any produced fines/sand; removing hydrocarbons orother organic contaminants from the produced brine by using settlingtanks and/or froth flotation and/or filtration; removing halites and/orother potential highly saturated salts or silica which don't possessretrograde solubilities by using a second crystallizer at reducedtemperature; or re-heating the brine before entering the electrochemicalcell to improve kinetics, reduce saturation indices and possiblyre-collect heat lost in the second, cooler crystallization step.
 8. Asystem to perform lithium extraction from lithium-containing brines,said system comprising: a cathodic tank allowing the insertion andremoval of electrode trays thereinto; and electrodes integrated into astack electrical system with connection to an anodic chamber to producean electrochemical cell.
 9. The system according to claim 8 operating ina semi-continuous or batch-wise manner.
 10. The system according toclaim 8, wherein the cathodic chamber is filled with lithium containingbrine.
 11. The system according to claim 8, wherein the anodic chamberis entirely or partially decoupled from the cathodic chamber such thatit has a distinct electrolyte composition not derived from the brine butinstead designed to conduct a particular anodic reaction on anappropriate anodic electrode surface.
 12. A system to perform lithiumextraction from lithium-containing brines, said system comprising: acathodic tank allowing the insertion and removal of electrode traysthereinto; a lithium-containing brine to be placed in the tank; and atleast one electrode integrated into a stack electrical system withconnection to an external energy source to produce an electrochemicalcell.
 13. A method of mass producing lithium-intercalated electrodesfrom a lithium-containing brine proximate the mining site of saidlithium-containing brine, said method comprising the steps of: obtainingsaid lithium-containing brine from a natural source; removingcontaminants from said lithium-containing brine; providing anelectrochemical cell comprising at least: a cathodic chamber; fillingthe cathodic chamber with said decontaminated lithium-containing brine;immersing a lithium-intercalating electrode into said decontaminatedlithium-containing brine in the cathodic tank; and applying anelectrical current to the electrochemical cell for a duration of timesufficient for lithium ions present in the lithium-containing brine tobe reduced and be deposited onto the electrode.
 14. The method accordingto claim 13, wherein the step of removing contaminants from saidlithium-containing brine comprises at least one of the operationsselected from the group consisting of: removing dissolved gases in theproduced fluid near the formation temperature in a crystallizer orsimilar vessel; precipitating saturated carbonates; removing anyproduced fines/sand; removing hydrocarbons or other organic contaminantsfrom the produced brine by using settling tanks and/or froth flotationand/or filtration; removing halites and/or other potential highlysaturated salts or silica which don't possess retrograde solubilities byusing a second crystallizer at reduced temperature; and re-heating thebrine before entering the electrochemical cell to improve kinetics,reduce saturation indices and possibly re-collect heat lost in thesecond, cooler crystallization step.